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This feature article introduces our recent work on understanding the roles played by citrate and poly(vinyl pyrrolidone) (PVP) as capping agents in seed-mediated syntheses of Ag nanocrystals with controlled shapes. We have demonstrated that citrate and PVP selectively bind to Ag(111) and Ag(100) surfaces, respectively, and thus favor the formation of Ag nanocrystals enclosed preferentially by {111} or {100} facets. In addition, we have quantified the coverage density of PVP adsorbed on the surface of Ag nanocubes. Based on the mechanistic understanding, a series of Ag nanocrystals with controlled shapes and sizes have been successfully synthesized by using different combinations of seeds and capping agents: single-crystal spherical/cubic seeds with citrate for cuboctahedrons and octahedrons or with PVP for cubes and bars; and plate-like seeds with citrate for enlarged thin plates or with PVP for thickened plates.

Recent Developments in Shape-Controlled Synthesis of Silver Nanocrystals